EP2621974B1 - Binder containing substituted benzenes and naphthalenes for producing cores and molds for metal casting, mold material mixture, and method - Google Patents

Binder containing substituted benzenes and naphthalenes for producing cores and molds for metal casting, mold material mixture, and method Download PDF

Info

Publication number
EP2621974B1
EP2621974B1 EP11801963.7A EP11801963A EP2621974B1 EP 2621974 B1 EP2621974 B1 EP 2621974B1 EP 11801963 A EP11801963 A EP 11801963A EP 2621974 B1 EP2621974 B1 EP 2621974B1
Authority
EP
European Patent Office
Prior art keywords
weight
alkyl
binder according
binder
dialkylated
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP11801963.7A
Other languages
German (de)
French (fr)
Other versions
EP2621974A1 (en
Inventor
Christian Priebe
Diether Koch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ASK Chemicals GmbH
Original Assignee
ASK Chemicals GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ASK Chemicals GmbH filed Critical ASK Chemicals GmbH
Publication of EP2621974A1 publication Critical patent/EP2621974A1/en
Application granted granted Critical
Publication of EP2621974B1 publication Critical patent/EP2621974B1/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C08G8/36—Chemically modified polycondensates by etherifying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
    • B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B22C1/2273—Polyurethanes; Polyisocyanates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
    • B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B22C1/2246—Condensation polymers of aldehydes and ketones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C1/00—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds
    • B22C1/16—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents
    • B22C1/20—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents
    • B22C1/22—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins
    • B22C1/2233—Compositions of refractory mould or core materials; Grain structures thereof; Chemical or physical features in the formation or manufacture of moulds characterised by the use of binding agents; Mixtures of binding agents of organic agents of resins or rosins obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B22C1/2246—Condensation polymers of aldehydes and ketones
    • B22C1/2253—Condensation polymers of aldehydes and ketones with phenols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C11/00—Moulding machines characterised by the relative arrangement of the parts of same
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0838—Manufacture of polymers in the presence of non-reactive compounds
    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0847—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers
    • C08G18/0852—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of solvents for the polymers the solvents being organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/54—Polycondensates of aldehydes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
    • C08G8/28—Chemically modified polycondensates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/01—Hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes

Definitions

  • the DE 102006037288 A1 discloses alkyl-substituted benzenes, alkyl-substituted naphthalenes and mixtures thereof as solvents for the isocyanate component.
  • the DE 102006037288 A1 does not disclose the required chain lengths of the alkyl / alkenyl radicals or boiling points, and does not disclose that they must be dialkyl substituted naphthalenes.
  • phenolic resins are known by the name "ortho-ortho” or “high-ortho” novolaks or benzyl ether resins. These are obtainable by condensation of phenols with aldehydes in weakly acidic medium using suitable catalysts.
  • Suitable catalysts for the preparation of benzylic ether resins are salts of divalent ions of metals such as Mn, Zn, Cd, Mg, Co, Ni, Fe, Pb, Ca and Ba.
  • zinc acetate is used.
  • the amount used is not critical. Typical amounts of metal catalyst are 0.02 to 0.3% by weight, preferably 0.02 to 0.15% by weight, based on the total amount of phenol and aldehyde.
  • Suitable polyisocyanates include aliphatic polyisocyanates, e.g. Hexamethylene diisocyanate, alicyclic polyisocyanates such as e.g. 4,4'-dicyclohexylmethane diisocyanate and dimethyl derivatives thereof.
  • suitable aromatic polyisocyanates are toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, xylylene diisocyanate and methyl derivatives thereof, as well as polymethylene polyphenyl isocyanates.
  • the phenolic resin component or the isocyanate component of the binder system is preferably used as a solution in an organic solvent or a combination of organic solvents.
  • Solvents may e.g. Therefore, to keep the components of the binder in a sufficiently low viscosity state. This is u. a. required to obtain a uniform crosslinking of the refractory molding material and its flowability.
  • oxygen-rich polar organic solvents can furthermore be used.
  • Particularly suitable are dicarboxylic acid esters, glycol ether esters, glycol diesters, glycol diethers, cyclic ketones, cyclic esters (lactones), cyclic carbonates or silicic acid esters or mixtures thereof.
  • Dicarboxylic acid esters, cyclic ketones and cyclic carbonates are preferably used.
  • fatty acid esters such as e.g. Rapeseed oil fatty acid methyl ester or oleic acid butyl ester.
  • Suitable silanes are, for example, aminosilanes, epoxysilanes, mercaptosilanes, hydroxysilanes and ureidosilanes, such as ⁇ -hydroxypropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, ⁇ -mercaptopropyltrimethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, ⁇ - (3,4-epoxycyclohexyl) trimethoxysilane and N-.beta. (aminoethyl) -y-aminopropyltrimethoxysilane.
  • the molded article produced by the process may per se have any shape customary in the field of foundry.
  • the shaped body is in the form of foundry molds or cores.
  • the invention relates to the use of this molding for metal casting, in particular iron and cast aluminum.

Description

Die vorliegende Erfindung betrifft ein Bindemittel auf Polyurethanbasis zur Herstellung von Kernen und Gießformen enthaltend Alkyl- / Alkenylbenzole und gleichzeitig dialkylierte und/oder dialkenylierte Naphthaline mit verzögerter Aushärtung der unkatalysierten Formstoffmischung, insbesondere für Cold-Box-Mischungen.The present invention relates to a polyurethane-based binder for the production of cores and casting molds containing alkyl / alkenylbenzenes and simultaneously dialkylated and / or dialkenylated naphthalenes with delayed curing of the uncatalyzed molding material mixture, in particular for cold box mixtures.

Die unter der Bezeichnung "Cold-Box-Verfahren" oder "Ashland-Verfahren" bekannt gewordene Methode der Kernherstellung hat in der Gießereiindustrie große Bedeutung erlangt. Zur Bindung eines feuerfesten Formgrundstoffes werden dabei Zwei-Komponenten-Polyurethan-Systeme eingesetzt. Die Polyol-Komponente besteht aus einem Polyol mit mindestens zwei OH-Gruppen pro Molekül, die Isocyanat-Komponente aus einem Polyisocyanat mit mindestens zwei NCO-Gruppen pro Molekül. Die Aushärtung des Bindemittelsystems erfolgt mit Hilfe von basischen Katalysatoren. Flüssige Basen können dem Bindemittelsystem vor der Formgebung zugemischt werden, um die beiden Komponenten zur Reaktion zu bringen ( US 3,676,392 ). Eine weitere Möglichkeit besteht darin, gasförmige tertiäre Amine nach der Formgebung durch das Formstoff-Bindemittelsystem-Gemisch ( US 3,409,579 ) zu leiten.The method known as "cold box process" or "Ashland process" has become very important in the foundry industry. Two-component polyurethane systems are used for bonding a refractory molding base material. The polyol component consists of a polyol having at least two OH groups per molecule, the isocyanate component of a polyisocyanate having at least two NCO groups per molecule. The curing of the binder system is carried out using basic catalysts. Liquid bases can be added to the binder system prior to molding to react the two components ( US 3,676,392 ). Another possibility is gaseous tertiary amines after shaping by the molding material-binder system mixture ( US 3,409,579 ).

Nach der US 3,676,392 und der US 3,409,579 werden Phenolharze als Polyole eingesetzt, die durch Kondensation von Phenol mit Aldehyden, vorzugsweise Formaldehyd, in flüssiger Phase bei Temperaturen bis ca. 130°C in Gegenwart katalytischer Mengen von Metallionen erhalten werden. In der US 3,485,797 wird die Herstellung solcher Phenolharze detailliert beschrieben. Außer unsubstituiertem Phenol können substituierte Phenole, vorzugsweise o-Kresol und p-Nonylphenol, zum Einsatz kommen (vergleiche z.B. US 4,590,229 ). Als weitere Reaktionskomponente werden nach der EP 0177871 A2 mit aliphatischen Monoalkohol-Gruppen mit ein bis acht Kohlenstoffatomen modifizierte Phenolharze eingesetzt. Durch die Alkoxylierung sollen die Bindemittelsysteme eine erhöhte thermische Stabilität besitzen.After US 3,676,392 and the US 3,409,579 Phenol resins are used as polyols obtained by condensation of phenol with aldehydes, preferably formaldehyde, in the liquid phase at temperatures up to about 130 ° C in the presence of catalytic amounts of metal ions. In the US 3,485,797 the preparation of such phenolic resins is described in detail. In addition to unsubstituted phenol, substituted phenols, preferably o-cresol and p-nonylphenol, can be used (compare, for example, US Pat US 4,590,229 ). As a further reaction component are after the EP 0177871 A2 used with aliphatic monoalcohol groups having one to eight carbon atoms modified phenolic resins. By alkoxylation, the binder systems should have increased thermal stability.

Die US 4590229 A offenbart als Lösungsmittel für ein Phenolharz als Komponente eine PU-Harzes innerhalb einer größeren Gruppe u.a. alkyl-substituierte Naphthalene (nach IUPAC, im Deutschen auch Naphthaline genannt), alkylsubstituierte Benzole und deren Mischungen aber keine Dialkyl(en)naphtalene und auch keine Kettenlängen der Alkylreste. Überdies ist der offenbarte Siedepunkt niedriger.The US 4590229 A discloses as a solvent for a phenolic resin as a component of a PU resin within a larger group, inter alia, alkyl-substituted naphthalenes (after IUPAC, in German also called naphthalenes), alkyl-substituted benzenes and mixtures thereof but no dialkyl (en) naphthalene and no chain lengths of the alkyl radicals , Moreover, the disclosed boiling point is lower.

Die US 4634758 A nennt Ethylbenzol und "heavy aromatic naphthas" als Lösungsmittel für die Hydroxy- und/oder die Isocyanat-Komponente. Naphtha ist hier aber als der technische Name für Rohbenzin zu verstehen und umfasst Paraffine, Cycloparaffine und weitere Kohlenwasserstoffe aber nicht Dialkylnaphthalen oder Dialkylennaphthalen, zumindest nicht ausdrücklich.The US 4634758 A mentions ethylbenzene and "heavy aromatic naphthas" as solvents for the hydroxy and / or the isocyanate component. However, naphtha is to be understood as the technical name for naphtha and includes paraffins, cycloparaffins and other hydrocarbons but not dialkyl naphthalene or dialkyl naphthalene, at least not expressly.

Die DE 102006037288 A1 offenbart alkyl-substituierte Benzole, alkyl-substituierte Naphthalene und deren Gemische als Lösungsmittel für die Isocyanat-Komponente. Die DE 102006037288 A1 offenbart jedoch nicht die erforderlichen Kettenlängen der Alkyl-/Alkenyl-Reste bzw. Siedepunkte und nicht, dass es sich um dialkylsubstituierte Naphthalene handeln muss.The DE 102006037288 A1 discloses alkyl-substituted benzenes, alkyl-substituted naphthalenes and mixtures thereof as solvents for the isocyanate component. The DE 102006037288 A1 however, does not disclose the required chain lengths of the alkyl / alkenyl radicals or boiling points, and does not disclose that they must be dialkyl substituted naphthalenes.

Die EP 1375028 A1 nennt lediglich allgemein hoch siedende aromatische Kohlenwasserstoffe wie Alkylbenzole, Xylole und Naphthalen als Lösungsmittel für die Isocyanat-Komponente. Für die Hydroxy-Komponente soll im Unterschied ein polares Lösungsmittel eingesetzt werden.The EP 1375028 A1 only generally mentions high-boiling aromatic hydrocarbons such as alkylbenzenes, xylenes and naphthalene as solvents for the isocyanate component. In contrast, a polar solvent should be used for the hydroxy component.

In den Beispielen der US 3632844 A wird lediglich aufgezeigt, dass aromatische Lösungsmittel eingesetzt werden können.In the examples of US 3632844 A it is only shown that aromatic solvents can be used.

Die obigen Offenbarungen für Lösungsmittel sind jeweils aber nicht gerichtet auf die nach der vorliegenden Erfindung gemeinsam erforderlichen längerkettigen Alkylaromaten und Dialkylnaphthalene. Überdies müssen diese nach der vorliegenden Erfindung nicht notwendig Lösungsmittel für die Hydroxy- und/oder die Isocyanat-Komponente sein.However, the above solvent disclosures are not directed to the longer chain alkyl aromatics and dialkylnaphthalenes commonly required in the present invention. Moreover, these need not necessarily be solvents for the hydroxy and / or the isocyanate component according to the present invention.

Als Lösemittel für die Polyol-Komponente werden überwiegend Gemische aus hochsiedenden polaren Lösemitteln (z.B. Ester und Ketone) und hochsiedenden aromatischen Kohlenwasserstoffen eingesetzt. Die Polyisocyanate werden dagegen bevorzugt in hochsiedenden aromatischen Kohlenwasserstoffen gelöst.As solvents for the polyol component predominantly mixtures of high-boiling polar solvents (for example, esters and ketones) and high-boiling aromatic hydrocarbons are used. On the other hand, the polyisocyanates are preferably dissolved in high-boiling aromatic hydrocarbons.

In der EP 0771599 A1 und der WO 00/25957 A1 werden Formulierungen beschrieben, bei denen durch Verwendung von Fettsäureestern ganz oder zumindest weitgehend auf aromatische Lösemittel verzichtet werden kann.In the EP 0771599 A1 and the WO 00/25957 A1 formulations are described in which by using fatty acid esters completely or at least largely can be dispensed with aromatic solvents.

Aus verschiedenen Gründen ist es wünschenswert, dass derartige Formstoffmischungen eine sehr lange Verarbeitungszeit besitzen, d.h. dass die beiden Komponenten nur dann miteinander reagieren, wenn sie in Kontakt mit einem Katalysator kommen. Auch wenn sich in dieser Hinsicht seit der Erfindung des "Cold-Box-Verfahrens" viel getan hat, z.B. durch die in US 4,540,724 beschriebene Zugabe von Phosphorhalogeniden zur Polyisocyanatkomponente, besitzen auch mit modernen Binderformulierungen hergestellte Formstoffmischungen eine begrenzte Lebensdauer. Dies macht sich dadurch bemerkbar, dass die Festigkeiten von Formen und Kernen mit zunehmendem Alter der Formstoffmischungen abnehmen und ab einem bestimmten Zeitpunkt den Wert für ein sicheres Handling und für ein gutes Gussergebnis unterschreiten. Die JP 3794944 B2 schlägt einen Zusatz an C6-C16-Alkylbenzolen vor, um das vorzeitige Aushärten der Formstoffmischung zu verhindern.For various reasons, it is desirable that such molding mixtures have a very long processing time, that is, that the two components react with each other only when they come in contact with a catalyst. Although much has been done in this regard since the invention of the "cold-box process", for example by the in US 4,540,724 described addition of phosphorus halides to the polyisocyanate component, even with modern binder formulations prepared molding mixtures have a limited life. This is noticeable by the fact that the strengths of molds and cores decrease with increasing age of the molding material mixtures and, at a certain point in time, fall below the value for safe handling and for a good casting result. The JP 3794944 B2 proposes an addition of C 6 -C 16 -alkylbenzenes to prevent the premature curing of the molding material mixture.

Als Konsequenz vorzeitigen Aushärtens müssen in der Praxis immer wieder größere Mengen unbrauchbar gewordener Formstoffmischungen entsorgt werden, z.B. nach unvorhergesehenen Produktionsunterbrechungen. Besonders hoch ist der Reinigungsaufwand von Maschinen, Vorrats- und Transportbehältern dann, wenn die Formstoffmischungen zum Zeitpunkt der Reinigung nicht mehr weich und fließfähig, sondern (teil)ausgehärtet sind.As a consequence of premature curing, in practice larger quantities of unusable molding material mixtures have to be disposed of, e.g. after unforeseen production stoppages. Particularly high is the cleaning of machinery, storage and transport containers when the molding material mixtures at the time of cleaning are no longer soft and flowable, but (partially) cured.

Von Seiten der Anwender besteht deshalb der Wunsch, Formstoffmischungen zur Verfügung gestellt zu bekommen, die nicht nur eine sehr lange Verarbeitungszeit besitzen, sondern die auch nach Ablauf der Verarbeitungszeit nicht zu einer festen Masse aushärten. Die Formstoffmischungen sollen auch dann noch weich und fließfähig sein, so dass die Kernschießmaschinen etc. leicht gereinigt werden können.There is therefore a desire on the part of the users to provide molding material mixtures which not only have a very long processing time, but which also do not harden to a solid mass after the end of the processing time. The molding material mixtures should then still be soft and flowable, so that the core shooting machines, etc. can be easily cleaned.

Der Erfindung lag daher die Aufgabe zu Grunde, den Gießereien eine Formstoffmischung für die Herstellung von Formkörpern zur Verfügung zu stellen, bei der die unkatalysierte Aushärtung nicht oder nur in einem sehr geringen Umfang eintritt, so dass die Mischung auch nach mehreren Stunden noch weich und fließfähig bleibt.The invention was therefore based on the object to provide the foundries with a molding material mixture for the production of moldings, in which the uncatalyzed curing does not occur or only to a very small extent, so that the mixture still soft and flowable even after several hours remains.

Es wurde nun überraschenderweise gefunden, dass durch den Zusatz von Alkyl- / Alkenylbenzolen in Verbindung mit dialkylierten und/oder dialkenylierten Naphthalinen gemäß Anspruch 1 die Aushärtung einer unkatalysierten Cold-Box-Mischung noch stärker verzögert wird als durch die gleiche Menge einer der beiden Substanzgruppen.It has now surprisingly been found that by the addition of alkyl / alkenylbenzenes in conjunction with dialkylated and / or dialkenylated naphthalenes according to claim 1, the curing of an uncatalyzed cold box mixture is retarded even more than by the same amount of one of the two substance groups.

Erfindungsgemäß weisen die Alkyl- und/oder Alkenylketten der Alkyl-/Alkenylbenzole und die dialkylierten / dialkenylierten Naphthaline unabhängig voneinander folgende Merkmale auf: Sie sind

  • geradzahlig oder ungeradzahlig;
  • gesättigt oder ungesättigt, vorzugsweise gesättigt, mit 8 bis 20 C-Atomen (Alkyl-/Alkenylbenzole) bzw. 2 bis 10 C-Atomen (dialkylierten / dialkenylierten Naphthaline);
  • verzweigt oder unverzweigt; und / oder
  • substituiert oder unsubstituiert, wobei die Substitution aus einem oder mehreren Phenylringen besteht.
According to the invention, the alkyl and / or alkenyl chains of the alkyl / alkenylbenzenes and the dialkylated / dialkenylated naphthalenes independently have the following characteristics: they are
  • even or odd;
  • saturated or unsaturated, preferably saturated, with 8 to 20 C atoms (alkyl / alkenylbenzenes) or 2 to 10 C atoms (dialkylated / dialkenylated naphthalenes);
  • branched or unbranched; and or
  • substituted or unsubstituted, wherein the substitution consists of one or more phenyl rings.

Der aromatische Grundkörper kann einfach oder mehrfach substituiert sein, wobei die Alkyl-/Alkenylsubstituenten am selben Grundkörper unterschiedlich sein können.The aromatic base may be monosubstituted or polysubstituted, where the alkyl / alkenyl substituents on the same body may be different.

Die Naphthaline sind dialkyliert und/oder dialkenyliert, vorzugsweise mit jeweils jeweils 2 bis 10 C-Atomen,wie z.B. Diisopropylnaphthalin.The naphthalenes are dialkylated and / or dialkenylated, preferably each having 2 to 10 C atoms, e.g. Diisopropylnaphthalene.

Die Gewichtsanteile Alkyl- / Alkenylbenzole (C) zu dialkylierten und/oder dialkenylierten Naphthalinen (D) verhalten sich relativ zueinander wie folgt C : D : 95 :5 bis 5 : 95, vorzugsweise 85 : 15 bis 15 bis 85, besonders bevorzugt 80 : 20 bis 20: 80The proportions by weight of alkyl / alkenylbenzenes (C) to dialkylated and / or dialkenylated naphthalenes (D) behave relative to one another as follows C: D: 95: 5 to 5:95, preferably 85: 15 to 15 to 85, particularly preferably 80: 20 to 20: 80

Gegenstand der Erfindung ist somit ein Bindemittel für Formstoffmischungen, z.B. in Form eines 2- oder Mehrkomponentensystems (A) plus (B), enthaltend

  1. (A) zumindest eine Polyol-Komponente aufweisend ein Polyol mit mindestens zwei OH-Gruppen pro Molekül, wobei die Polyol-Komponente zumindest ein Phenolharz umfasst, und
  2. (B) zumindest eine Isocyanat-Komponente aufweisend ein Polyisocyanat mit mindestens.zwei NCO-Gruppen pro Molekül und
  3. (C) zumindest ein Alkyl- / Alkenylbenzol mit einem nach DIN 51761 gemessenen Siedepunkt größer 250°C und besonders bevorzugt größer 260°C oder sogar größer 270°C und
  4. (D) zumindest ein dialkyliertes und/oder dialkenyliertes Naphthalin mit einem Siedepunkt größer 270°C
neben u.a. ggf. einem oder mehreren weiteren Komponenten wie Lösemitteln bzw. Additiven. Die Siedebereiche schließen Substanzen ein, die sich zersetzen bevor sie sieden.The invention thus relates to a binder for molding material mixtures, for example in the form of a 2- or multi-component system (A) plus (B) containing
  1. (A) at least one polyol component comprising a polyol having at least two OH groups per molecule, wherein the polyol component comprises at least one phenolic resin, and
  2. (B) at least one isocyanate component comprising a polyisocyanate having at least. Two NCO groups per molecule and
  3. (C) at least one alkyl / alkenylbenzene having a boiling point of more than 250 ° C. and particularly preferably greater than 260 ° C. or even greater than 270 ° C. measured according to DIN 51761 and
  4. (D) at least one dialkylated and / or dialkenylated naphthalene having a boiling point greater than 270 ° C.
in addition, inter alia, if necessary, one or more other components such as solvents or additives. The boiling areas include substances that decompose before they boil.

Die Komponenten (C) und (D) sowie etwaige weitere Komponenten wie Lösemittel bzw. Additive bilden insbesondere jeweils unabhängig voneinander einen Bestandteil von entweder (A), (B) oder (A) und (B). Die Komponente (C) und (D) ist vorzugsweise bei Raumtemperatur (20°C) flüssig.;In particular, the components (C) and (D) as well as any further components such as solvents or additives in each case independently form a constituent of either (A), (B) or (A) and (B). The component (C) and (D) is preferably liquid at room temperature (20 ° C .;

Gegenstand der Erfindung sind weiterhin Formstoffmischungen gemäß Anspruch 15 und ein Verfahren zur Herstellung eines Gießformteils oder eines Kerns, gemäß Anspruch 16. Bevorzugte Ausführungsformen sind jeweils Gegenstand der Unteransprüche oder nachfolgend beschrieben.The invention further molding material mixtures according to claim 15 and a method for producing a mold part or a core, according to claim 16. Preferred embodiments are each subject of the dependent claims or described below.

Der Anteil der Kombination Alkyl-/Alkenylbenzol und dialkyliertes/dialkenyliertes Naphthalin im Bindemittel (in Bezug auf das gesamte Bindemittel einschließlich etwaiger weiterer Zusatzstoffe, wie Lösemitteln, Silane und sonstige Additive) beträgt 1 bis 25 Gew.%, bevorzugt 1 bis 20 Gew.% und besonders bevorzugt 1 bis 15 Gew.%.The proportion of the combination of alkyl / alkenylbenzene and dialkylated / dialkenylated naphthalene in the binder (with respect to the entire binder, including any further additives, such as solvents, silanes and other additives) is 1 to 25% by weight, preferably 1 to 20% by weight. and particularly preferably 1 to 15% by weight.

Nach einer Ausführungsform weisen die Alkyl- und/oder Alkenyl-Reste des/der Alkyl-/ Alkenylbenzole jeweils bevorzugt 8 bis 20 C-Atome und die Reste des/der dialkylierten und/oder dialkenylierten Naphthaline insbesondere jeweils 2 bis 10 C-Atome auf und sind gesättigt oder ungesättigt, vorzugsweise gesättigt.According to one embodiment, the alkyl and / or alkenyl radicals of the alkyl / alkenylbenzenes each preferably have 8 to 20 C atoms and the radicals of the dialkylated and / or dialkenylated naphthalenes in particular in each case 2 to 10 C atoms and are saturated or unsaturated, preferably saturated.

Die Alkyl-/Alkenylbenzole können monoalkylierte Benzole mit einer gesättigten Alkylkette von 8 bis 20 C-Atomen sein oder enthalten, während die dialkylierten/dialkenylierten Naphthaline bevorzugt dialkylierte Naphthaline sind mit vorzugsweise jeweils 2 bis 10 C-Atomen je Alkyl-/Alkenylrest.The alkyl / alkenylbenzenes may be or contain monoalkylated benzenes having a saturated alkyl chain of 8 to 20 carbon atoms, while the dialkylated / dialkenylated naphthalenes are preferably dialkylated naphthalenes having preferably 2 to 10 carbon atoms per alkyl / alkenyl radical.

Die Gewichtsanteile Alkyl- / Alkenylbenzole zu alkylierten und/oder alkenylierten Naphthalinen verhalten sich nach einer Ausführungsform relativ zueinander wie 95 :5 bis 5 : 95 vorzugsweise wie 85 : 15 bis 15 : 85, besonders bevorzugt wie 80 : 20 bis 20 : 80.The proportions by weight of alkyl / alkenylbenzenes to alkylated and / or alkenylated naphthalenes in one embodiment are relatively as 95: 5 to 5:95, preferably 85:15 to 15:85, more preferably 80:20 to 20:80.

Ein geeignetes Alkyl- / Alkenylbenzol ist z.B. das Handelsprodukt Marlican® der Firma Sasol Germany GmbH.A suitable alkyl / alkenylbenzene is e.g. the commercial product Marlican® the company Sasol Germany GmbH.

Ein geeignetes dialkyliertes und/oder dialkenyliertes Naphthalin ist z.B. das Handelsprodukt Rütasolv® DI der Firma Rütgers Kureha Solvents GmbH.A suitable dialkylated and / or dialkenylated naphthalene is e.g. the commercial product Rütasolv® DI Rütgers Kureha Solvents GmbH.

Der Begriff "alkyliert und/oder alkenyliert" bzw. "Alkyl- / Alkenyl-" schließt jeweils Gruppen ein die mehrfach Aryl-substituiert sind wie Alkylidene (Beispiel -(CH2)m-) oder Alkenylidene (Beispiel: -(CH2)m-CH=CH-(CH2)o-).The term "alkylated and / or alkenylated" or "alkyl / alkenyl" respectively includes groups which are multiple aryl-substituted, such as alkylidenes (example - (CH 2 ) m -) or alkenylidenes (example: - (CH 2 ) m is -CH = CH- (CH 2 ) o -).

Weiterhin betrifft die Erfindung Formstoffmischungen, die feuerfeste Formgrundstoffe und bis zu 5 Gew.%, bevorzugt bis zu 4 Gew.%, besonders bevorzugt bis zu 3 Gew.% des erfindungsgemäßen Bindemittelsystems, bezogen auf das Gewicht der feuerfesten Formgrundstoffe, umfassen.Furthermore, the invention relates to molding material mixtures which comprise refractory molding base materials and up to 5% by weight, preferably up to 4% by weight, particularly preferably up to 3% by weight, of the binder system according to the invention, based on the weight of the refractory molding base materials.

Als feuerfeste Formgrundstoffe können dabei beispielsweise Quarz-, Zirkon- oder Chromerzsand, Olivin, Schamotte und Bauxit verwendet werden. Weiterhin können auch synthetisch hergestellte Formgrundstoffe verwendet werden, wie z.B. Aluminiumsilikathohlkugeln (sog. Microspheres), Glasperlen, Glasgranulat oder die unter der Bezeichnung "Cerabeads" bzw. "Carboaccucast" bekannten kugelförmigen keramischen Formgrundstoffe. Mischungen der genannten Feuerfeststoffe sind ebenfalls möglich.For example, quartz, zirconium or chrome ore, olivine, chamotte and bauxite can be used as refractory mold bases. Furthermore, synthetically prepared mold bases may also be used, e.g. Aluminum silicate hollow spheres (so-called microspheres), glass beads, glass granules or the spherical ceramic molding base materials known by the name "Cerabeads" or "Carboaccucast". Mixtures of said refractories are also possible.

Die Erfindung betrifft ebenfalls ein Verfahren zur Herstellung eines Gießformteils oder eines Kerns, umfassend

  1. (a) Vermischen von Feuerfeststoffen mit dem erfindungsgemäßen Bindemittelsystem in einer bindenden Menge von 0,2 bis 5 Gew.%, bevorzugt 0,3 bis 4 Gew.%, besonders bevorzugt 0,4 bis 3 Gew.%, bezogen auf die Menge der Feuerfeststoffe, zum Erhalt eines Gießgemisches;
  2. (b) Einbringen des in Schritt (a) erhaltenen Gießgemisches in ein Formwerkzeug;
  3. (c) Härten des Gießgemisches im Formwerkzeug, um ein selbsttragendes Gießformteil zu erhalten; und
  4. (d) anschließendes Trennen des gehärteten Gießgemisches vom Werkzeug und ggf. weiteres Härten, wodurch man ein hartes, festes, ausgehärtetes Gießformteil erhält.
The invention also relates to a method for producing a foundry part or a core comprising
  1. (A) mixing of refractory materials with the binder system according to the invention in a binding amount of 0.2 to 5 wt.%, Preferably 0.3 to 4 wt.%, Particularly preferably 0.4 to 3 wt.%, Based on the amount of Refractories, to obtain a casting mixture;
  2. (b) introducing the casting mixture obtained in step (a) into a molding tool;
  3. (c) curing the cast mix in the mold to obtain a self-supporting mold part; and
  4. (d) subsequently separating the cured casting mixture from the tool and optionally further curing, thereby obtaining a hard, solid, cured casting part.

Die Polyolkomponente weist Phenol-Aldehyd-Harze auf, hier vorliegend verkürzt Phenolharze genannt. Zur Herstellung der Phenolharze sind alle herkömmlich verwendeten Phenol-Verbindungen geeignet. Neben unsubstituierten Phenolen können substituierte Phenole oder Gemische hiervon eingesetzt werden. Die Phenol-Verbindungen sind vorzugsweise entweder in beiden ortho-Positionen oder in einer ortho- und in der para-Position nicht substituiert. Die verbleibenden Ring-Kohlenstoffatome können substituiert sein. Die Wahl des Substituenten ist nicht besonders beschränkt, sofern der Substituent die Reaktion des Phenols mit dem Aldehyd nicht nachteilig beeinflusst. Beispiele substituierter Phenole sind alkylsubstituierte, alkoxysubstituierte, arylsubstituierte und aryloxysubstituierte Phenole.The polyol component comprises phenol-aldehyde resins, here abbreviated called phenolic resins. For the preparation of the phenolic resins, all conventionally used phenolic compounds are suitable. In addition to unsubstituted phenols, substituted phenols or mixtures thereof can be used. The phenolic compounds are preferably unsubstituted either in both ortho positions or in an ortho and in the para position. The remaining ring carbon atoms may be substituted. The choice of the substituent is not particularly limited so long as the substituent does not adversely affect the reaction of the phenol with the aldehyde. Examples of substituted phenols are alkyl-substituted, alkoxy-substituted, aryl-substituted and aryloxy-substituted phenols.

Die vorstehend genannten Substituenten haben beispielsweise 1 bis 26, bevorzugt 1 bis 15 Kohlenstoffatome. Beispiele geeigneter Phenole sind o-Kresol, m-Kresol, p-Kresol, 3,5-Xylenol, 3,4-Xylenol, 3,4,5-Trimethylphenol, 3-Ethylphenol, 3,5-Diethylphenol, p-Butylphenol, 3,5-Dibutylohenol, p-Amylphenol, Cyclohexylphenol, p-Octylphenol, p-Nonylphenol, Cardanol, 3,5-Dicyclohexylphenol, p-Crotylphenol, p-Phenylphenol, 3,5-Dimethoxyphenol und p-Phenoxyphenol.The abovementioned substituents have, for example, 1 to 26, preferably 1 to 15, carbon atoms. Examples of suitable phenols are o-cresol, m-cresol, p-cresol, 3,5-xylenol, 3,4-xylenol, 3,4,5-trimethylphenol, 3-ethylphenol, 3,5-diethylphenol, p-butylphenol, 3,5-Dibutylohenol, p-amylphenol, cyclohexylphenol, p-octylphenol, p-nonylphenol, cardanol, 3,5-dicyclohexylphenol, p-crotylphenol, p-phenylphenol, 3,5-dimethoxyphenol and p-phenoxyphenol.

Besonders bevorzugt ist Phenol selbst. Auch höher kondensierte Phenole, wie Bisphenol A, sind geeignet. Darüber hinaus eignen sich auch mehrwertige Phenole, die mehr als eine phenolische Hydroxylgruppe aufweisen.Particularly preferred is phenol itself. Also higher condensed phenols, such as bisphenol A, are suitable. In addition, polyhydric phenols having more than one phenolic hydroxyl group are also suitable.

Bevorzugte mehrwertige Phenole weisen 2 bis 4 phenolische Hydroxylgruppen auf. Spezielle Beispiele geeigneter mehrwertiger Phenole sind Brenzkatechin, Resorcin, Hydrochinon, Pyrogallol, Phloroglucin, 2,5-Dimethylresorcin, 4,5-Dimethylresorcin, 5-Methylresorcin oder 5-Ethylresorcin. Es können auch Gemische aus verschiedenen ein- und mehrwertigen und/oder substituierten und/oder kondensierten Phenolkomponenten für die Herstellung der Polyolkomponente verwendet werden.Preferred polyhydric phenols have 2 to 4 phenolic hydroxyl groups. Specific examples of suitable polyhydric phenols are pyrocatechol, resorcinol, hydroquinone, pyrogallol, phloroglucinol, 2,5-dimethylresorcinol, 4,5-dimethylresorcinol, 5-methylresorcinol or 5-ethylresorcinol. Mixtures of various mono- and polyhydric and / or substituted and / or condensed phenolic components can also be used for the preparation of the polyol component.

In einer Ausführungsform werden Phenole der allgemeinen Formel I:

Figure imgb0001
zur Herstellung der Phenolharzkomponente verwendet, wobei A, B und C unabhängig voneinander ausgewählt sind aus: Einem Wasserstoffatom, einem verzweigten oder unverzweigten Alkylrest, der beispielsweise 1 bis 26, vorzugsweise 1 bis 15 Kohlenstoffatome aufweisen kann, einem verzweigten oder unverzweigten Alkoxyrest, der beispielsweise 1 bis 26, vorzugsweise 1 bis 15 Kohlenstoffatome aufweisen kann, einem verzweigten oder unverzweigten Alkenoxyrest, der beispielsweise 1 bis 26, vorzugsweise 1 bis 15 Kohlenstoffatome aufweisen kann, einem Aryl- oder Alkylarylrest, wie beispielsweise Bisphenyle.In one embodiment, phenols of general formula I:
Figure imgb0001
 used for the preparation of the phenolic resin component, wherein A, B and C are independently selected from: a hydrogen atom, a branched or unbranched alkyl radical which may have, for example 1 to 26, preferably 1 to 15 carbon atoms, a branched or unbranched alkoxy radical, for example 1 to 26, preferably 1 to 15 carbon atoms, a branched or unbranched alkenoxy, which may for example have 1 to 26, preferably 1 to 15 carbon atoms, an aryl or alkylaryl, such as bisphenols.

Als Aldehyd zur Herstellung der Phenolharzkomponente eignen sich Aldehyde der Formel:

        R-CHO,

wobei R ein Wasserstoffatom oder ein Kohlenstoffatomrest mit vorzugsweise 1 bis 8, besonders bevorzugt 1 bis 3 Kohlenstoffatomen ist. Spezielle Beispiele sind Formaldehyd, Acetaldehyd, Propionaldehyd, Furfurylaldehyd und Benzaldehyd. Besonders bevorzugt wird Formaldehyd eingesetzt, entweder in seiner wässrigen Form, als para-Formaldehyd, oder Trioxan.Suitable aldehydes for the production of the phenolic resin component are aldehydes of the formula:

R-CHO,

wherein R is a hydrogen atom or a carbon atom radical having preferably 1 to 8, particularly preferably 1 to 3 carbon atoms. Specific examples are formaldehyde, acetaldehyde, propionaldehyde, furfuraldehyde and benzaldehyde. Particularly preferably, formaldehyde is used, either in its aqueous form, as para-formaldehyde, or trioxane.

Um die Phenolharze zu erhalten, wird vorzugsweise eine mindestens äquivalente Molzahl an Aldehyd, bezogen auf die Molzahl der Phenolkomponente, eingesetzt. Bevorzugt beträgt das Molverhältnis Aldehyd zu Phenol 1 : 1,0 bis 2,5: 1, besonders bevorzugt 1,1 : 1 bis 2,2 : 1, insbesondere bevorzugt 1,2 : 1 bis 2,0 : 1.In order to obtain the phenolic resins, it is preferable to use an at least equivalent number of moles of aldehyde, based on the number of moles of the phenol component. The molar ratio of aldehyde to phenol is preferably 1: 1.0 to 2.5: 1, more preferably 1.1: 1 to 2.2: 1, particularly preferably 1.2: 1 to 2.0: 1.

Die Herstellung des Phenolharzes erfolgt nach dem Fachmann bekannten Verfahren. Dabei werden das Phenol und der Aldehyd unter im Wesentlichen wasserfreien Bedingungen, insbesondere in Gegenwart eines zweiwertigen Metall-ions, bei Temperaturen von vorzugsweise weniger als 130°C umgesetzt. Das entstehende Wasser wird abdestilliert. Dazu kann der Reaktionsmischung ein geeignetes Schleppmittel zugesetzt werden, beispielsweise Toluol oder Xylol, oder die Destillation wird bei reduziertem Druck durchgeführt.The preparation of the phenolic resin is carried out by methods known in the art. In this case, the phenol and the aldehyde are reacted under substantially anhydrous conditions, in particular in the presence of a divalent metal ion, at temperatures of preferably less than 130 ° C. The resulting water is distilled off. For this purpose, the reaction mixture, a suitable entraining agent may be added, for example toluene or xylene, or the distillation is carried out at reduced pressure.

Das Phenolharz wird so gewählt, dass eine Vernetzung mit der PolyisocyanatKomponente möglich ist. Für den Aufbau eines Netzwerkes sind Phenolharze, die Moleküle mit mindestens zwei Hydroxylgruppen im Molekül umfassen, notwendig.The phenolic resin is chosen so that crosslinking with the polyisocyanate component is possible. For building a network, phenolic resins comprising molecules having at least two hydroxyl groups in the molecule are necessary.

Besonders geeignete Phenolharze sind unter der Bezeichnung "ortho-ortho"' oder "high-ortho"-Novolake bzw. Benzyletherharze bekannt. Diese sind durch Kondensation von Phenolen mit Aldehyden in schwach saurem Medium unter Verwendung geeigneter Katalysatoren erhältlich. Zur Herstellung von Benzyletherharzen geeignete Katalysatoren sind Salze zweiwertiger Ionen von Metallen, wie Mn, Zn, Cd, Mg, Co, Ni, Fe, Pb, Ca und Ba. Bevorzugt wird Zinkacetat verwendet. Die eingesetzte Menge ist nicht kritisch. Typische Mengen an Metallkatalysator betragen 0,02 bis 0,3 Gew.%, bevorzugt 0,02 bis 0,15 Gew.%, bezogen auf die Gesamtmenge an Phenol und Aldehyd.Particularly suitable phenolic resins are known by the name "ortho-ortho" or "high-ortho" novolaks or benzyl ether resins. These are obtainable by condensation of phenols with aldehydes in weakly acidic medium using suitable catalysts. Suitable catalysts for the preparation of benzylic ether resins are salts of divalent ions of metals such as Mn, Zn, Cd, Mg, Co, Ni, Fe, Pb, Ca and Ba. Preferably, zinc acetate is used. The amount used is not critical. Typical amounts of metal catalyst are 0.02 to 0.3% by weight, preferably 0.02 to 0.15% by weight, based on the total amount of phenol and aldehyde.

Solche Harze sind z.B. in US 3,485,797 und in EP 1137500 B1 beschrieben, auf deren Offenbarung hiermit sowohl hinsichtlich der Harze selbst, als auch hinsichtlich ihrer Herstellung ausdrücklich Bezug genommen wird.Such resins are eg in US 3,485,797 and in EP 1137500 B1 The disclosure of which is hereby expressly incorporated by reference both to the resins themselves and to their preparation.

Die Isocyanat- Komponente des Bindemittelsystems umfasst ein aliphatisches, cycloaliphatisches oder aromatisches Polyisocyanat, bevorzugt mit 2 bis 5 Isocyanatgruppen pro Molekül. Je nach den gewünschten Eigenschaften können auch Gemische von Isocyanaten eingesetzt werden.The isocyanate component of the binder system comprises an aliphatic, cycloaliphatic or aromatic polyisocyanate, preferably having 2 to 5 isocyanate groups per molecule. Depending on the desired properties, it is also possible to use mixtures of isocyanates.

Geeignete Polyisocyanate umfassen aliphatische Polyisocyanate, wie z.B. Hexamethylendiisocyanat, alicyclische Polyisocyanate wie z.B. 4,4'-Dicyclohexylmethandiisocyanat und Dimethylderivate hiervon. Beispiele geeigneter aromatischer Polyisocyanate sind Toluol-2,4-diisocyanat, Toluol-2,6-diisocyanat, 1,5-Naphthalendiisocyanat, Triphenylmethantriisocyanat, Xylylendiisocyanat und Methylderivate hiervon, sowie Polymethylenpolyphenylisocyanate. Insbesondere bevorzugte Polyisocyanate sind aromatische Polyisocyanate, besonders bevorzugt sind Polymethylenpolyphenylpolyisocyanate wie z.B. technisches 4,4'-Diphenylmethandiisocyanat, d.h. 4,4'-Diphenylmethandiisocyanat mit einem Anteil an Isomeren und höheren Homologen.Suitable polyisocyanates include aliphatic polyisocyanates, e.g. Hexamethylene diisocyanate, alicyclic polyisocyanates such as e.g. 4,4'-dicyclohexylmethane diisocyanate and dimethyl derivatives thereof. Examples of suitable aromatic polyisocyanates are toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, 1,5-naphthalene diisocyanate, triphenylmethane triisocyanate, xylylene diisocyanate and methyl derivatives thereof, as well as polymethylene polyphenyl isocyanates. Particularly preferred polyisocyanates are aromatic polyisocyanates, particularly preferred are polymethylene polyphenyl polyisocyanates such as e.g. technical 4,4'-diphenylmethane diisocyanate, i. 4,4'-diphenylmethane diisocyanate with a proportion of isomers and higher homologs.

Die Phenolharzkomponente bzw. die Isocyanatkomponente des Bindemittelsystems wird bevorzugt als Lösung in einem organischen Lösemittel oder einer Kombination von organischen Lösemitteln eingesetzt. Lösemittel können z.B. deshalb erforderlich sein, um die Komponenten des Bindemittels in einem ausreichend niedrigviskosen Zustand zu halten. Dieser ist u. a. erforderlich, um eine gleichmäßige Vernetzung des feuerfesten Formstoffes und dessen Rieselfähigkeit zu erhalten.The phenolic resin component or the isocyanate component of the binder system is preferably used as a solution in an organic solvent or a combination of organic solvents. Solvents may e.g. Therefore, to keep the components of the binder in a sufficiently low viscosity state. This is u. a. required to obtain a uniform crosslinking of the refractory molding material and its flowability.

Als Lösemittel für die Phenolharzkomponente können neben den z.B. unter der Bezeichnung Solvent Naphtha bekannten aromatischen Lösemitteln weiterhin sauerstoffreiche polare, organische Lösemittel verwendet werden. Geeignet sind vor allem Dicarbonsäureester, Glykoletherester, Glykoldiester, Glykoldiether, cyclische Ketone, cyclische Ester (Lactone), cyclische Carbonate oder Kieselsäureester oder deren Mischungen. Bevorzugt werden Dicarbonsäureester, cyclische Ketone und cyclische Carbonate verwendet.As solvents for the phenolic resin component, in addition to the aromatic solvents known, for example, under the name of solvent naphtha, oxygen-rich polar organic solvents can furthermore be used. Particularly suitable are dicarboxylic acid esters, glycol ether esters, glycol diesters, glycol diethers, cyclic ketones, cyclic esters (lactones), cyclic carbonates or silicic acid esters or mixtures thereof. Dicarboxylic acid esters, cyclic ketones and cyclic carbonates are preferably used.

Der Anteil der sauerstoffreichen polaren Lösemitteln am Gesamtbindemittel kann 0 bis 30 Gew.%, insbesondere 1 bis 30 Gew.%, betragen.The proportion of oxygen-rich polar solvents in the total binder may be from 0 to 30% by weight, in particular from 1 to 30% by weight.

Bevorzugte Dicarbonsäureester weisen die Formel R1OOC-R2-COOR1 auf, wobei R1 jeweils unabhängig voneinander eine Alkylgruppe mit 1 bis 12, bevorzugt 1 bis 6, Kohlenstoffatomen darstellt und R2 eine Alkylengruppe mit 1 bis 4 Kohlenstoffatomen ist. Beispiele sind Dimethylester von Carbonsäuren mit 4 bis 6 Kohlenstoffatomen, die z.B. unter der Bezeichnung Dibasic Ester von DuPont erhältlich sind. Ebenso sind Phthalate geeignet.Preferred dicarboxylic acid esters have the formula R 1 OOC-R 2 -COOR 1 , wherein each R 1 is independently an alkyl group having 1 to 12, preferably 1 to 6, carbon atoms and R 2 is an alkylene group having 1 to 4 carbon atoms. Examples are dimethyl esters of carboxylic acids having 4 to 6 carbon atoms which are obtainable, for example, under the name Dibasic Ester from DuPont. Likewise, phthalates are suitable.

Bevorzugte Glykoletherester sind Verbindungen der Formel R3-O-R4-OOCR5, wobei R3 eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen darstellt, R4 eine Alkylengruppe mit 2 bis 4 Kohlenstoffatomen ist und R5 eine Alkylgruppe mit 1 bis 3 Kohlenstoffatomen ist, z.B. Butylglykolacetat, bevorzugt sind Glykoletheracetate.Preferred glycol ether esters are compounds of the formula R 3 -OR 4 -OOCR 5 where R 3 is an alkyl group of 1 to 4 carbon atoms, R 4 is an alkylene group of 2 to 4 carbon atoms and R 5 is an alkyl group of 1 to 3 carbon atoms, eg Butyl glycol acetate, preferred are glycol ether acetates.

Bevorzugte Glykoldiester weisen entsprechend die allgemeine Formel R3COO-R4-OOCR5 auf, wobei R3 bis R5 wie oben definiert sind und die Reste jeweils unabhängig voneinander ausgewählt werden (z.B. Propylenglykoldiacetat). Bevorzugt sind Glykoldiacetate. Glykoldiether lassen sich durch die Formel R3-O-R4-O-R5 charakterisieren, in der R3 bis R5 wie oben definiert sind und die Reste jeweils unabhängig voneinander ausgewählt werden (z.B, Dipropylenglykoldimethylether).Preferred glycol diesters correspondingly have the general formula R 3 COO-R 4 -OOCR 5 , where R 3 to R 5 are as defined above and the radicals are each selected independently of one another (for example propylene glycol diacetate). Preferred are glycol diacetates. Glycol diethers can be characterized by the formula R 3 -OR 4 -OR 5 in which R 3 to R 5 are as defined above and the radicals are each selected independently of one another (for example, dipropylene glycol dimethyl ether).

Bevorzugte Cyclische Ketone, cyclische Ester und cyclische Carbonate mit 4 bis 5 Kohlenstoffatomen sind ebenfalls geeignet (z.B. Propylencarbonat). Die Alkyl- und Alkylengruppen können jeweils verzweigt oder unverzweigt sein.Preferred cyclic ketones, cyclic esters and cyclic carbonates of 4 to 5 carbon atoms are also suitable (e.g., propylene carbonate). The alkyl and alkylene groups may each be branched or unbranched.

Bevorzugte sind auch Fettsäurester wie z.B. Rapsölfettsäuremethylester oder Ölsäurebutylester.Preferred are also fatty acid esters such as e.g. Rapeseed oil fatty acid methyl ester or oleic acid butyl ester.

Als Lösemittel für das Polyisocyanat werden entweder aromatische Lösemittel, die oben genannten polaren Lösemittel oder Gemische davon, eingesetzt. Auch Fettsäureester und Kieselsäureester sind geeignet.The solvents used for the polyisocyanate are either aromatic solvents, the abovementioned polar solvents or mixtures thereof. Also fatty acid esters and silicic acid esters are suitable.

Neben den bereits erwähnten Bestandteilen können die Bindemittelsysteme Zusätze enthalten, z. B. Silane (z.B. gemäß EP 1137500 B1 ) oder interne Trennmittel, z. B. Fettalkohole (z.B. gemäß US 4,602,069 ), trocknende Öle (z.B. gemäß US 4,268,425 ) oder Komplexbildner (z.B. gemäß US 5,447,968 ) oder Gemische davon.In addition to the components already mentioned, the binder systems may contain additives, for. B. silanes (eg according to EP 1137500 B1 ) or internal release agents, for. B. fatty alcohols (eg according to US 4,602,069 ), drying oils (eg according to US 4,268,425 ) or complexing agents (eg according to US 5,447,968 ) or mixtures thereof.

Geeignete Silane sind beispielsweise Aminosilane, Epoxysilane, Mercaptosilane, Hydroxysilane und Ureidosilane, wie γ-Hydroxypropyltrimethoxysilan, γ-Amino-propyltrimethoxysilan, 3-Ureidopropyltriethoxysilan, γ-Mercaptopropyltrimethoxy-silan, γ-Glycidoxypropyltrimethoxysilan, ß-(3,4-Epoxycyclohexyl)trimethoxysilan und N-ß-(Aminoethyl)-y-aminopropyltrimethoxysilan.Suitable silanes are, for example, aminosilanes, epoxysilanes, mercaptosilanes, hydroxysilanes and ureidosilanes, such as γ-hydroxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) trimethoxysilane and N-.beta. (aminoethyl) -y-aminopropyltrimethoxysilane.

Für die Herstellung der Formstoffmischung können zuerst die Komponenten des Bindemittelsystems vereinigt und dann zu dem feuerfesten Formgrundstoff zugegeben werden. Es ist jedoch auch möglich, die Komponenten des Bindemittels gleichzeitig oder nacheinander zu dem feuerfesten Formgrundstoff zu geben.For the preparation of the molding material mixture, the components of the binder system can first be combined and then added to the refractory molding material. However, it is also possible to add the components of the binder simultaneously or sequentially to the refractory base molding material.

Bevorzugt wird das Polyisocyanat in einer Menge eingesetzt, dass die Anzahl der Isocyanatgruppen von 80 bis 120 %, bezogen auf die Anzahl der freien Hydroxylgruppen des Harzes, beträgt.Preferably, the polyisocyanate is used in an amount such that the number of isocyanate groups is from 80 to 120%, based on the number of free hydroxyl groups of the resin.

Um eine gleichmäßige Mischung der Komponenten der Formstoffmischung zu erzielen, können übliche Verfahren verwendet werden. Die Formstoffmischung kann zusätzlich gegebenenfalls andere konventionelle Bestandteile, wie Eisenoxid, gemahlene Flachsfasern, Holzmehlgranulate, Pech und refraktäre Metalle enthalten.To obtain a uniform mixture of the components of the molding material mixture, conventional methods can be used. In addition, the molding material mixture may optionally contain other conventional ingredients such as iron oxide, milled flax fibers, wood flour granules, pitch and refractory metals.

Als weiteren Gegenstand betrifft die Erfindung ein Verfahren zur Herstellung eines Formkörpers, mit den Schritten:

  • Bereitstellen der oben beschriebenen Formstoffmischung;
  • Ausformen der Formstoffmischung zu einem Formkörper;
  • Aushärten des Formkörpers durch Zugabe eines Aushärtungskatalysators.
As a further subject matter, the invention relates to a process for producing a shaped body, comprising the steps:
  • Providing the molding compound mixture described above;
  • Molding the molding material mixture into a shaped body;
  • Curing the molding by adding a curing catalyst.

Zur Herstellung des Formkörpers wird zunächst wie oben beschrieben das Bindemittel mit dem feuerfesten Formgrundstoff zu einer Formstoffmischung vermischt. Soll die Herstellung des Formkörpers nach dem PU-No-Bake-Verfahren erfolgen, kann der Formstoffmischung auch bereits ein geeigneter Katalysator zugegeben werden. Bevorzugt werden dazu flüssige Amine zur Formstoffmischung gegeben. Diese Amine weisen bevorzugt einen pKb-Wert von 4 bis 11 auf. Beispiele geeigneter Katalysatoren sind 4-Alkylpyridine, wobei die Alkylgruppe 1 bis 4 Kohlenstoffatome umfasst, Isochinolin, Arylpyridine, wie Phenylpyridin, Pyridin, 2-Methoxypyridin, Pyridazin, Chinolin, n-Methylimidazol, 4,4'-Dipyridin, Phenylpropylpyridin, 1-Methylbenzimidazol, 1,4-Thiazin, N,N-Dimethylbenzylamin, Triethylamin, Tribenzylamin, N,N-Dimethyl-1,3-Propandiamin, N,N-Dimethylethanolamin sowie Triethanolamin. Der Katalysator kann gegebenenfalls mit einem inerten Lösemittel verdünnt werden, beispielsweise 2,2,4-Trimethyl-1,3-pentandiol-diisobutyrat, oder einem Fettsäureester. Die Menge des zugegebenen Katalysators wird, bezogen auf das Gewicht der Polyolkomponente, im Bereich von 0,1 bis 15 Gew.% gewählt.For the production of the molded article, the binder is first mixed with the refractory molding base material to form a molding material mixture as described above. If the molding is to be produced by the PU-No-Bake process, a suitable catalyst can also already be added to the molding material mixture. For this purpose, liquid amines are preferably added to the molding material mixture. These amines preferably have a pK b value of 4 to 11. Examples of suitable catalysts are 4-alkylpyridines wherein the alkyl group comprises 1 to 4 carbon atoms, isoquinoline, arylpyridines such as phenylpyridine, pyridine, 2-methoxypyridine, pyridazine, quinoline, n-methylimidazole, 4,4'-dipyridine, phenylpropylpyridine, 1-methylbenzimidazole , 1,4-thiazine, N, N-dimethylbenzylamine, triethylamine, tribenzylamine, N, N-dimethyl-1,3-propanediamine, N, N-dimethylethanolamine and triethanolamine. The catalyst may optionally be diluted with an inert solvent, for example 2,2,4-trimethyl-1,3-pentanediol diisobutyrate, or a fatty acid ester. The amount of catalyst added is selected in the range of 0.1 to 15 weight percent, based on the weight of the polyol component.

Die Formstoffmischung wird dann mit üblichen Mitteln in eine Form eingebracht und dort verdichtet. Die Formstoffmischung wird anschließend zu einem Formkörper ausgehärtet. Bei der Härtung sollte der Formkörper bevorzugt seine äußere Form behalten.The molding material mixture is then introduced by conventional means into a mold and compacted there. The molding material mixture is then cured to a shaped body. When curing, the shaped body should preferably retain its outer shape.

Gemäß einer weiteren bevorzugten Ausführungsform erfolgt die Aushärtung nach dem PU-Cold-Box-Verfahren. Dazu wird ein gasförmiger Katalysator durch die geformte Formstoffmischung geleitet. Als Katalysator können die üblichen Katalysatoren auf dem Gebiet des Cold-Box-Verfahrens verwendet werden. Besonders bevorzugt werden Amine als Katalysatoren verwendet, insbesondere bevorzugt Dimethylethylamin, Dimethyl-n-propylamin, Dimethylisopropylamin, Dimethyl-n-butylamin, Triethylamin und Trimethylamin in ihrer gasförmigen Form oder als Aerosol.According to a further preferred embodiment, the curing takes place according to the PU cold box method. For this purpose, a gaseous catalyst is passed through the molded molding material mixture. As catalyst, the usual catalysts in the field of cold-box process can be used. Particular preference is given to using amines as catalysts, in particular preferably dimethylethylamine, dimethyl-n-propylamine, dimethylisopropylamine, dimethyl-n-butylamine, triethylamine and trimethylamine in their gaseous form or as aerosol.

Der mit dem Verfahren hergestellte Formkörper kann an sich jede auf dem Gebiet der Gießerei übliche Form aufweisen. In einer bevorzugten Ausführungsform liegt der Formkörper in Form von Gießereiformen oder -kernen vor.The molded article produced by the process may per se have any shape customary in the field of foundry. In a preferred embodiment, the shaped body is in the form of foundry molds or cores.

Weiter betrifft die Erfindung einen Formkörper, wie er mit dem oben beschriebenen Verfahren erhalten werden kann. Dieser zeichnet sich durch eine hohe mechanische Stabilität aus.Furthermore, the invention relates to a shaped body, as can be obtained by the method described above. This is characterized by a high mechanical stability.

Weiter betrifft die Erfindung die Verwendung dieses Formkörpers für den Metall-guss, insbesondere Eisen- sowie Aluminiumguss.Furthermore, the invention relates to the use of this molding for metal casting, in particular iron and cast aluminum.

Die Erfindung wird im Weiteren anhand von bevorzugten Ausführungsformen bzw. näher Versuchsbeispielen erläutert.The invention is explained below with reference to preferred embodiments or closer experimental examples.

BeispieleExamples

Es wurden die in Tab. 1 aufgeführten Polyisocyanatlösungen hergestellt (jeweils in Gew.%, Summe = 100): Tabelle 1 Vergleichsversuche erfindungsgemäß 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 techn. polymeres MDI 80 80 80 80 80 80 80 80 Solvent Naphtha leicht a) 10 10 10 10 10 Marlican b) 20 10 10 5 7,5 2,5 Rütasolv DI c) 20 10 10 5 2,5 7,5 a.) Aral Aromatics GmbH (CAS 64742-95-6), Siedepunkt 165-180°C
b.) Alkylbenzol (C10-C16), Sasol Germany GmbH
c.) Diisopropylnaphthalin, Rütgers Kureha Solvents GmbH The polyisocyanate solutions listed in Tab. 1 were prepared (in each case in% by weight, total = 100): Table 1 Comparative tests inventively 1.1 1.2 1.3 1.4 1.5 1.6 1.7 1.8 techn. polymeric MDI 80 80 80 80 80 80 80 80 Solvent naphtha easily a) 10 10 10 10 10 Marlican b) 20 10 10 5 7.5 2.5 Rütasolv DI c) 20 10 10 5 2.5 7.5 a.) Aral Aromatics GmbH (CAS 64742-95-6), boiling point 165-180 ° C
b.) Alkylbenzene (C 10 -C 16 ), Sasol Germany GmbH
c.) Diisopropylnaphthalene, Rütgers Kureha Solvents GmbH

Herstellung der Formstoffmischungen Beispiele 1 bis 3Preparation of the molding material mixtures Examples 1 to 3

Jeweils 0,8 Gewichtsteile des handelsüblichen, keine aromatischen Lösemittel enthaltenden Cold-Box-Binders Teil 1 Ecocure 300 WM 10 (ASK Chemicals GmbH) wurden mit jeweils 0,8 Gewichtsteilen der in Tab. 1 aufgeführten Isoccyanatlösungen 1.1, 1.2 und 1.5 sowie 100 Gewichtsteilen Quarzsand H 32 (Quarzwerke Frechen GmbH) in einem Labormischer der Fa. Vogel & Schemmann intensiv vermischt.In each case 0.8 parts by weight of the commercially available cold-box binder, which contains no aromatic solvents, Part 1 Ecocure 300 WM 10 (ASK Chemicals GmbH) were each containing 0.8 part by weight of the isocyanate solutions 1.1, 1.2 and 1.5 listed in Table 1 and 100 parts by weight Quartz sand H 32 (Quarzwerke Frechen GmbH) was thoroughly mixed in a laboratory mixer from Vogel & Schemmann.

Von jeder Mischung wurden jeweils 200 g in Probengläser (Volumen 370 ml, Durchmesser 6 cm) gefüllt und diese fest verschlossen. Durch einmaliges Aufklopfen der Gläser auf den Labortisch wurden die Mischungen leicht verdichtet. Nach festgelegten Zeiten wurden die Gläser geöffnet und umgedreht. Die Menge des auslaufenden Sandes wurde gewogen; sie diente als Maß für die Fließfähigkeit der gelagerten Formstoffmischung. Die Ergebnisse sind in Tab. 2 zusammengefasst.200 g of each mixture were filled into test tubes (volume 370 ml, diameter 6 cm) and tightly closed. The mixtures were lightly compacted by simply tapping the glasses on the laboratory bench. After specified times, the glasses were opened and turned over. The amount of leaking sand was weighed; it served as a measure of the flowability of the stored molding material mixture. The results are summarized in Tab. 2.

Aus Tab. 2 erkennt man, dass die Kombination aus Alkylbenzol und Dialkylnaphthalin die Formstoffmischung länger fließfähig hält als jede der beiden Substanzen für sich. Tabelle 2 Vergleichsversuche erfindungsgemäß Bsp. 1 2 3 Teil 1 Ecocure 300 WM 10 Ecocure 300 WM 10 Loser Sand [g] nach Teil 2 1.1 1.2 1.5 3 Std. 120 117 178 5 Std. 87 109 164 7 Std. 0 98 136 From Table 2 it can be seen that the combination of alkylbenzene and dialkylnaphthalene keeps the molding material mixture longer flowable than either of the two substances alone. Table 2 Comparative tests inventively Ex. 1 2 3 Part 1 Ecocure 300 WM 10 Ecocure 300 WM 10 Loose sand [g] after Part 2 1.1 1.2 1.5 3 hours. 120 117 178 5 hours 87 109 164 7 hours 0 98 136

Beispiele 4 bis 8Examples 4 to 8

Der Test wurde mit den Isocyanatlösungen 1.3, 1.4, 1.6, 1.7 und 1.8 wiederholt. Die Ergebnisse sind in Tab. 3 zusammengefasst. Tabelle 3 Vergleichsversuche erfindungsgemäß Bsp. 4 5 6 7 8 Teil 1 Ecocure 300 WM 10 Ecocure 300 WM 10 Loser Sand [g] nach Teil 2 1.3 1.4 1.6 1.7 1.8 5 Std. 160 144 193 182 184 7 Std. 127 130 180 166 182 12 Std. 0 0 170 145 135 The test was repeated with the isocyanate solutions 1.3, 1.4, 1.6, 1.7 and 1.8. The results are summarized in Tab. 3. Table 3 Comparative tests inventively Ex. 4 5 6 7 8th Part 1 Ecocure 300 WM 10 Ecocure 300 WM 10 Loose sand [g] after Part 2 1.3 1.4 1.6 1.7 1.8 5 hours 160 144 193 182 184 7 hours 127 130 180 166 182 12 hours 0 0 170 145 135

Aus Tab. 3 erkennt man, dass die Kombination aus Alkylbenzol und Dialkylnaphthalin auch in Isocyanatlösungen, die ein weiteres Lösemittel enthalten, die Formstoffmischungen länger fließfähig hält als jede der beiden Substanzen für sich.From Table 3 it can be seen that the combination of alkylbenzene and dialkylnaphthalene, even in isocyanate solutions containing another solvent, keeps the molding material mixtures more fluid than either of the two substances per se.

Beispiele 9 bis 13Examples 9 to 13

Der Test wurde mit dem handelsüblichen, ein aromatisches Lösemittel enthaltenden Cold-Box-Binder Teil 1 Askocure 366 (ASK Chemicals) wiederhott. Die Ergebnisse sind in Tab. 4 zusammengefasst. Tabelle 4 nicht erfindungsgemäß erfindungsgemäß Bsp. 9 10 11 12 13 Teil 1 Askocure 366 Askocure 366 Loser Sand [g] nach Teil 2 1.3 1.4 1.6 1.7 1.8 5 Std. 127 114 155 184 172 7 Std. 0 108 136 92 93 10 St. 0 40 105 83 84 12 Std. 0 0 75 45 43 The test was repeated with the commercially available aromatic-containing cold box binder, Part 1, Askocure 366 (ASK Chemicals). The results are summarized in Tab. 4. Table 4 not according to the invention inventively Ex. 9 10 11 12 13 Part 1 Askocure 366 Askocure 366 Loose sand [g] after Part 2 1.3 1.4 1.6 1.7 1.8 5 hours 127 114 155 184 172 7 hours 0 108 136 92 93 10 hours 0 40 105 83 84 12 hours 0 0 75 45 43

Aus Tab. 4 erkennt man, dass die Kombination aus Alkylbenzol und Alkylnaphthalin auch mit dem ein aromatisches Lösemittel enthaltendes Cold-Box-Binder Teil 1 die Formstoffmischung länger fließfähig hält als jede der beiden Substanzen für sich.From Tab. 4 it can be seen that the combination of alkylbenzene and alkylnaphthalene with the aromatic-solvent-containing cold box binder Part 1 keeps the molding material mixture longer flowable than either of the two substances alone.

Claims (21)

  1. A binder for mold material mixtures, containing
    (A) at least one phenolic resin component as the polyol component comprising a phenolic resin, wherein the phenolic resin is obtainable from the reaction between a phenol compound and an aldehyde compound,
    (B) at least one isocyanate component containing at least one polyisocyanate with at least two NCO groups per molecule, and
    (C) at least one alkyl/alkenyl benzene with a boiling point above 250 °C, and
    (D) at least one dialkylated and/or dialkenylated naphthalene with a boiling point above 270 °C.
  2. The binder according to claim 1, characterized in that the one or more alkyl and/or alkenyl radicals of the alkyl/alkenyl benzene(s) has/have 8 to 20 C atoms, and the radicals of the dialkylated and/or dialkenylated naphthalene(s) each has/have 2 to 10 C atoms, and are saturated or unsaturated, preferably saturated.
  3. The binder according to claim 1 or 2, characterized in that the alkyl/alkenyl benzenes are monoalkylated benzenes with a saturated alkyl chain of 8 to 20 C atoms.
  4. The binder according to at least one of the preceding claims, characterized in that the dialkylated and/or dialkenylated naphthalenes each comprise 2 to 6 C atoms for each alkyl/alkenyl radical independently of each other.
  5. The binder according to at least one of the preceding claims, characterized in that the weight proportions of alkyl/alkenyl benzenes to dialkylated and/or dialkenylated naphthalenes are in the following ratios to each other: 95 : 5 to 5 : 95, preferably 85 : 15 to 15 to 85, particularly preferably 80 : 20 to 20 : 80.
  6. The binder according to at least one of the preceding claims, characterized in that the proportion of alkyl/alkenyl benzenes and dialkylated/dialkenylated naphthalenes in combination is 1 to 25% by weight, preferably 1 to 20% by weight, and particularly preferably 1 to 15% by weight in the binder.
  7. The binder according to claim 1, wherein the polyisocyanate is an aromatic polyisocyanate, particularly a polymethylene polyphenyl polyisocyanate.
  8. The binder according to claim 1, wherein the phenolic resin is obtainable by reacting a phenol compound with an aldehyde compound in a weakly acidic medium and using transition metal catalysts, particularly zinc catalysts.
  9. The binder according to claim 8, wherein the catalyst is a zinc compound, particularly zinc acetate dihydrate.
  10. The binder according to claim 1, wherein the phenolic resin is a benzylether resin.
  11. The binder according to claim 1 or 8, wherein the phenol compound is selected from one or more members of the following group: phenol, o-cresol, p-cresol, bisphenol A or cardanol.
  12. The binder according to claim 1 or 8, wherein the aldehyde compound is an aldehyde having formula:

            R-CHO,

    wherein R stands for a hydrogen atom or a carbon radical having preferably 1 to 8, particularly preferably 1 to 3 carbon atoms.
  13. The binder according to one or more of the preceding claims, wherein the components (A) to (D) are contained in the binder as follows:
    (A) 15 to 35% by weight, particularly 20 to 30% by weight phenolic resin,
    (B) 25 to 45% by weight, particularly 35 to 45% by weight polyisocyanate, and
    (C)+(D) 1 to 25% by weight, particularly 1 to 15% by weight alkyl/alkenyl benzene in conjunction with at least one dialkylated and/or dialkenylated naphthalene.
  14. The binder according to one or more of the preceding claims, wherein additional aromatic hydrocarbons, oxygen-rich, polar, organic solvents, esters, ketones and/or plasticizers, particularly additional aromatic hydrocarbons, oxygen-rich, polar, organic solvents together, are used as a further solvent.
  15. The binder according to one or more of the preceding claims, wherein 1 to 30% by weight oxygen-rich, polar, organic solvents are used as a further solvent.
  16. The binder according to one or more of the preceding claims, wherein the binder is in the form of a 2- or multiple component system and at least one component is component (A) and at least one other component is component (B) and preferably the at least one alkyl/alkenyl benzene and/or the at least one dialkylated and/or dialkenylated naphthalene are constituents of the respective components (A) and/or (B) independently of one another.
  17. The binder according to one or more of the preceding claims, wherein
    a) the alkyl/alkenyl benzene has a boiling point higher than 260 °C, and
    b) independently thereof the dialkylated and/or dialkenylated naphthalene has a boiling point higher than 270 °C.
  18. A mold material mixture comprising the binder according to one or more of the preceding claims and a refractory mold material, wherein the mold material contains or consists of silicon dioxide for example in the form of quartz sand, zirconium sand or chromium sand, olivine, refractory clay, bauxite, aluminum silicate hollow spheres, glass beads, granulated glass, and/or synthetic ceramic mold base materials.
  19. A method for producing a casting mold element or a core, comprising:
    (a) mixing refractory materials with the binder according to any of claims 1 to 17 in a quantity from 0.2 to 5% by weight, preferably 0.3 to 4% by weight, particularly preferably 0.4 to 3% by weight, relative to the quantity of the refractory materials, to obtain a casting mixture;
    (b) introducing the casting mixture into a molding tool;
    (c) hardening the casting mixture in the molding tool to obtain a self-supporting mold; and
    (d) subsequently separating the hardened casting mold element from the tool, and optionally hardening further to obtain a solid, cured casting mold element.
  20. The method according to claim 19, wherein dimethyl ethylamine, dimethyl-n-propylamine, dimethyl isopropylamine, dimethyl-n-butylamine, triethylamine and/or trimethylamine is used for curing, each being used as a gas or an aerosol.
  21. The method according to claim 19, wherein a liquid catalyst, particularly phenylpropyl pyridine is used for curing.
EP11801963.7A 2010-09-30 2011-09-30 Binder containing substituted benzenes and naphthalenes for producing cores and molds for metal casting, mold material mixture, and method Active EP2621974B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102010046981A DE102010046981A1 (en) 2010-09-30 2010-09-30 Binder containing substituted benzenes and naphthalenes for the production of cores and molds for metal casting, molding mix and process
PCT/DE2011/001789 WO2012041294A1 (en) 2010-09-30 2011-09-30 Binder containing substituted benzenes and naphthalenes for producing cores and molds for metal casting, mold material mixture, and method

Publications (2)

Publication Number Publication Date
EP2621974A1 EP2621974A1 (en) 2013-08-07
EP2621974B1 true EP2621974B1 (en) 2015-11-18

Family

ID=45418275

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11801963.7A Active EP2621974B1 (en) 2010-09-30 2011-09-30 Binder containing substituted benzenes and naphthalenes for producing cores and molds for metal casting, mold material mixture, and method

Country Status (10)

Country Link
US (1) US9000067B2 (en)
EP (1) EP2621974B1 (en)
JP (1) JP6023714B2 (en)
KR (1) KR20130099134A (en)
CN (1) CN103140524B (en)
BR (1) BR112013007732A2 (en)
DE (1) DE102010046981A1 (en)
EA (1) EA023742B1 (en)
MX (1) MX342047B (en)
WO (1) WO2012041294A1 (en)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102775568B (en) * 2012-07-27 2014-04-09 山东圣泉化工股份有限公司 Preparation method of modified phenolic resin
DE102013106276A1 (en) * 2013-06-17 2014-12-18 Ask Chemicals Gmbh Lithium-containing molding material mixtures based on an inorganic binder for the production of molds and cores for metal casting
CN104014714B (en) * 2014-05-29 2015-12-30 朱小英 A kind of aluminum alloy cast moulding sand
CN104014747B (en) * 2014-05-29 2016-04-20 朱小英 A kind of technique of gravitational casting turbocharger air compressor shell
DE102014110189A1 (en) * 2014-07-18 2016-01-21 Ask Chemicals Gmbh CO catalysts for polyurethane cold box binders
DE102016115947A1 (en) * 2016-08-26 2018-03-01 Ask Chemicals Gmbh Process for the layered construction of moldings with a phenolic resin-polyurethane-based binder system
DE102016125700A1 (en) * 2016-12-23 2018-06-28 Ask Chemicals Gmbh Benzyl ether-type phenol resin-based binder containing free phenol and hydroxybenzyl free alcohols
DE102016125624A1 (en) * 2016-12-23 2018-06-28 HÜTTENES-ALBERTUS Chemische Werke Gesellschaft mit beschränkter Haftung Phenolic resin for use in the phenolic resin component of a two component binder system
CN106694794B (en) * 2017-03-14 2020-07-03 山东科技大学 Triethylamine cold core box binder

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3485797A (en) 1966-03-14 1969-12-23 Ashland Oil Inc Phenolic resins containing benzylic ether linkages and unsubstituted para positions
US3429848A (en) 1966-08-01 1969-02-25 Ashland Oil Inc Foundry binder composition comprising benzylic ether resin,polyisocyanate,and tertiary amine
US3632844A (en) * 1969-03-10 1972-01-04 Ashland Oil Inc Non-sticking sand mix for foundry cores
US3676392A (en) 1971-01-26 1972-07-11 Ashland Oil Inc Resin compositions
US4079031A (en) * 1976-07-14 1978-03-14 Delta Oil Products Corporation Improved foundry process and binder resin composition therefor
US4268425A (en) 1979-05-14 1981-05-19 Ashland Oil, Inc. Phenolic resin-polyisocyanate binder systems containing a drying oil and use thereof
US4420643A (en) * 1982-09-30 1983-12-13 American Cyanamid Company Extraction of phenols from aqueous solutions
JPS60136737A (en) * 1983-12-22 1985-07-20 Fuji Photo Film Co Ltd Silver halide photographic printing paper
US4540724A (en) 1984-01-30 1985-09-10 Ashland Oil Inc. Phenolic resin-polyisocyanate binder systems containing a phosphorus halide and use thereof
US4602069A (en) 1984-04-11 1986-07-22 Ashland Oil, Inc. Phenolic resin-polyisocyanate binder systems containing a phosphorus based acid
US4590229A (en) 1984-06-04 1986-05-20 Ashland Oil, Inc. Phenolic resin-polyisocyanate binder systems
US4546124A (en) * 1984-10-12 1985-10-08 Acme Resin Corporation Polyurethane binder compositions
US4634758A (en) * 1984-10-12 1987-01-06 Acme Resin Corporation Process for preparing alkoxy-modified phenolic resole resins
DE3445687A1 (en) * 1984-12-14 1986-06-19 Hüttenes-Albertus Chemische Werke GmbH, 4000 Düsseldorf UNDER POLYURETHANE FORMING COLD-MOLDING MOLD BINDER SYSTEM
US5447968A (en) 1993-07-23 1995-09-05 Ashland Inc. Polyurethane-forming binder systems containing 2,2'-dipyridyl, 1,10-phenanthroline, and their substituted alkyl derivatives
SI0771599T2 (en) 1995-11-01 2004-04-30 Huettenes-Albertus Binder based on polyurethanes for producing foundry mould and core compositions
US5874487A (en) * 1996-11-07 1999-02-23 Ashland Inc. Foundary binder systems which contain alcohol modified polyisocyanates
JP3913298B2 (en) * 1996-11-08 2007-05-09 株式会社クラレ Method for producing microcapsules
US6288139B1 (en) * 1998-09-24 2001-09-11 Ashland Inc. Foundry binder system containing an ortho ester and their use
DE19850833C2 (en) 1998-11-04 2001-06-13 Ashland Suedchemie Kernfest Binder system for the production of cores and molds based on polyurethane, their use and method for producing a mold part based on polyurethane
US6429236B1 (en) * 2000-05-23 2002-08-06 Ashland Inc. Acrylic-modified phenolic-urethane foundry binders
JP3794944B2 (en) 2000-07-31 2006-07-12 保土谷アシュランド株式会社 Manufacturing method of casting mold
DE10205065A1 (en) * 2002-02-07 2003-08-21 Ashland Suedchemie Kernfest Compositions containing cyclopentadiene adducts and their use for chemical resistant coatings
ITMI20021258A1 (en) * 2002-06-10 2003-12-10 Cavenaghi Spa FOUNDRY BINDING SYSTEMS
US20050256288A1 (en) * 2004-05-13 2005-11-17 Zhenya Zhu High performance polyurethanes cured with alkylated 4,4'-methylenedianiline
JP4537347B2 (en) * 2006-05-23 2010-09-01 アシュランドジャパン株式会社 Binder composition for mold production, composition for mold production, and casting mold production method
DE102006037288B4 (en) * 2006-08-09 2019-06-13 Ask Chemicals Gmbh Molding material mixture containing Cardol and / or Cardanol in foundry binders based on polyurethane, process for the preparation of a molded article and use thereof
US20080207795A1 (en) * 2007-01-19 2008-08-28 Henry Colleen M Binder Formulations Utilizing Furanic Components
ES2739455T3 (en) * 2007-01-22 2020-01-31 Arkema France Process for manufacturing cast iron forming cores and for casting metals

Also Published As

Publication number Publication date
WO2012041294A1 (en) 2012-04-05
BR112013007732A2 (en) 2017-09-26
CN103140524B (en) 2016-05-04
JP2013540863A (en) 2013-11-07
KR20130099134A (en) 2013-09-05
US20130299120A1 (en) 2013-11-14
MX2013003378A (en) 2013-07-29
CN103140524A (en) 2013-06-05
EP2621974A1 (en) 2013-08-07
EA201390402A1 (en) 2013-09-30
EA023742B1 (en) 2016-07-29
US9000067B2 (en) 2015-04-07
DE102010046981A1 (en) 2012-04-05
JP6023714B2 (en) 2016-11-09
MX342047B (en) 2016-09-12

Similar Documents

Publication Publication Date Title
EP2621974B1 (en) Binder containing substituted benzenes and naphthalenes for producing cores and molds for metal casting, mold material mixture, and method
EP2640764B2 (en) Binder based on polyurethane for producing cores and moulds using isocyanates containing a urethonimine and/or carbodiimide group, a mould material mixture containing said binder, and a method for using said binder
EP2598550B1 (en) Binder system based on polyurethane for producing cores and casting molds using cyclic formaldehydes, molding material mixture, and method
EP1137500B1 (en) Binder system for producing polyurethane-based cores and moulds
EP3558560B1 (en) Binder based on phenolic resins of the benzyl ether type, containing free phenol and free hydroxybenzyl alcohols
DE102006037288B4 (en) Molding material mixture containing Cardol and / or Cardanol in foundry binders based on polyurethane, process for the preparation of a molded article and use thereof
WO2019137583A1 (en) Phenolic resin binder with reduced formadehyde content
DE102015107016A1 (en) Process for reducing free formaldehyde in benzyl ether resins
WO2016008467A1 (en) Co-catalysts for polyurethane cold box binders
DE102013004663B4 (en) Binder system, molding material mixture containing the same, process for producing the molding material mixture, process for producing a mold part or casting core, mold part or casting core and use of the mold part or casting core thus obtainable for metal casting
EP3333205B1 (en) Polyurethane binder with improved flowability
EP3558559B1 (en) Component system for producing cores and molds
EP3265254B1 (en) Method for curing a polyurethane binders in moulding material mixtures by introducing tertiary amines, and solvents and kit for implementation of the method
DE102014117284A1 (en) Polyurethane binder system for producing cores and casting molds, molding material mixture containing the binder and a method using the binder
WO2014146940A1 (en) Use of carboxylic acids and fatty amines in pu-binders for producing cores and moulds for metal casting

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20130424

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20140417

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20150216

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20150714

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 761537

Country of ref document: AT

Kind code of ref document: T

Effective date: 20151215

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: GERMAN

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 502011008373

Country of ref document: DE

Representative=s name: MUELLER SCHUPFNER & PARTNER PATENT- UND RECHTS, DE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 502011008373

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20160218

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160218

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160318

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160318

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160219

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 502011008373

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20160819

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20160930

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20170531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160930

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160930

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160930

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160930

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160930

REG Reference to a national code

Ref country code: AT

Ref legal event code: MM01

Ref document number: 761537

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160930

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20160930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20110930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151118

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230517

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20231129

Year of fee payment: 13